Process for recycling bleach plant filtrate

ABSTRACT

A process for bleaching wood pulp is provided comprising subjecting the wood pulp, after brown stock washing, to an oxygen delignification stage, a washing sequence, a first chlorine dioxide bleaching stage, an oxidative extraction stage, at least one final chlorine dioxide bleaching stage and then recycling the filtrate from the oxidative extraction stage countercurrently through the bleaching plant and brown stock washing. Additionally, and quite beneficially, the filtrate from the first chlorine dioxide bleaching stage is also recycled countercurrently through the brown stock washing thereby significantly reducing the environmental impact associated with the manufacture of bleach wood pulp.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of application Ser. No.873,673, filed Apr. 24, 1992, now abandoned, which, in turn, is acontinuation of application Ser. No. 646,179, filed Jan. 28, 1991, nowabandoned.

FIELD OF THE INVENTION

This invention relates to an improved method for recycling bleachfiltrates. More particularly, this invention relates to improvements inthe bleaching process including a recycling process for reducing theenvironmental impact associated with the manufacture of bleached woodpulp.

BACKGROUND OF THE INVENTION

The process of the present invention is applicable to any cellulosicfibrous material but is described with particular reference to thebleaching of wood pulp, preferably wood pulp produced by the Kraftprocess, i.e., wood pulp produced by digestion of wood chips in thepulping liquor containing sodium hydroxide and sodium sulfide as theactive pulping chemicals. Following the wood digestion process, pulp isseparated from the spent pulping liquor. The spent pulping liquor isthen recovered and regenerated for recycling.

The Kraft process wood pulp is then bleached and purified in a bleachplant operation. In the bleach, plant, pulp is first subjected tooxidizing chemicals such as chlorine and/or chlorine dioxide andfollowed by extraction with a suitable source of alkali such as sodiumhydroxide. Depending on the desired pulp brightness, one to threeadditional bleaching stages are employed with typically one being analkali extraction stage and one or two stages using oxidizing chemicals.Following each bleaching stage, spent bleaching chemicals are removedfrom the pulp by washing with a suitable source of water; either freshwater or previously used water from pulp washing or a combination of thetwo. Current state of the art requires that all wash water from thebleach plant along with spent bleaching chemicals be discharged to thesewer as effluents rather than being processed in the pulping liquorregeneration operation noted above. Various concerns have prevented therecovery of these bleach plant effluents in the pulping liquorregeneration operation. One concern is the possible build-up ofchlorides causing corrosion and operational problems. Another concern isthe lack of adequate systems for removing non-process metals, such ascalcium, magnesium and manganese, which enter the bleach plant and aretypically removed with wash water and spent bleach chemicals.

Further, the use of large volumes of water for pulp washing in thebleach plant has also prevented recovery of bleach plant effluents dueto the resulting high evaporator load. The environmental impact of thesepractices has been widely noted, but despite these serious concerns, theability to overcome the problems associated with recovery as describedabove has not been developed.

In the 1970's, the closed mill concept for recovering bleach planteffluents developed by Rapson, U.S. Pat. No. 3,698,995, and laterimproved by Reeve et al. in U.S. Pat. No. 4,039,372 was tested at GreatLakes Papers in Thunder Bay, Ontario. The mill began operation in 1977but was abandoned in 1985. The mill attempted to reduce the discharge ofthe bleach plant effluent by recycling the filtrates to the pulpingliquor regeneration process. The bleaching process employed was(D/C)EDED. The process included a salt crystallization system as a meansof purging sodium chloride. The chloride levels introduced into thepulping liquor regeneration process were within the range of 90-100lbs/adt pulp. With the crystallization process, the concentration inwhite liquor was equal to or in excess of 50 grams per liter beforeequilibrium was reached, i.e., chloride entering is equal to the amountof chloride removed.

This process was unsuccessful in the recovery of the bleach plantfiltrates. The reasons for this were related to continued concerns ofcorrosion, pulp quality, inadequate removal of non-process metals andhigh evaporation requirements.

After the experience at Thunder Bay, Reeve noted the following featuresas needing to be developed for the success of future effluent-freemills: low chloride concentrations in the recovery process; a chlorideremoval system employing minimal evaporation; low bleach filtrate flowto minimize evaporation requirements, a bleaching sequence thatminimizes bleach chemical consumption due to recycle of extractedorganic components; and adequate systems to remove minor wood componentssuch as potassium, calcium and pitch.

Substituting chlorine dioxide for chlorine and incorporating oxygendelignification in the bleach sequence reduces the chloride content ofthe bleach effluent when compared to sequences without oxygen andchlorine dioxide. Use of the ODED sequence, referenced in U.S. Pat. No.4,039,372, for recovering bleach plant filtrates would reduce the sodiumchloride input to the recovery process by 73% over that experienced atThunder Bay during closed mill operation. While use of the ODED bleachsequence would represent a significant reduction in chloride content ofthe bleach filtrate streams compared to Thunder Bay's closed millexperience, the resulting chloride content of black liquor feeding therecovery boiler would cause operating problems. The chloride content ofblack liquor feeding the recovery boiler is a function not only of thequantity of chloride introduced to the recovery process but also theprocess used to remove chlorides. A significant fraction of the chloridefeeding the recovery boiler is the result of chloride accumulation inthe ash that is volatilized in the boiler, collected and returned to theboiler feed. Potassium, which also affects recovery boiler operation,accumulates in the boiler ash in a similar manner. At Thunder Bay,sodium chloride was removed from the recovery process by evaporation andcrystallization of sodium chloride from white liquor. This chlorideremoval process not only represents a significant increase in theevaporation load of a mill, it also does not prevent the large cyclicflow of sodium chloride and potassium compounds contained in therecovery boiler ash which represents a significant fraction of thechloride and potassium load to the recovery boiler.

U.S. Pat. No. 4,039,372 by Reeve et al. shows that 1895 gallons perminute of bleach filtrate is recovered from a 500 T/D bleach plant andsent to the pulp mill/recovery operation. All liquor recovered from thebleach plant must be evaporated. The flow of 1895 gallons per minuterepresents more than twice the normal volumetric flow needed for brownstock washing. According to U.S. Pat. No. 4,039,372, a portion of the1895 gallons per minute is used for diluting white liquor that isconcentrated during the sodium chloride removal operation. The netresult is a nearly doubling of the evaporation load of the mill. Themost significant factor contributing to the large filtrate flow from thebleach plant in U.S. Pat. No. 4,039,372 is the use of fresh water towash pulp at two locations in the bleach plant.

Various metals such as calcium, magnesium, manganese and potassium enterthe pulp mill with the wood supply. These metals if not adequatelypurged from the pulping and bleaching operations can cause operatingproblems. In current operations these metals are released from the pulpin the first acidic stage of the bleach plant due to the low pH (2-3) ofoperation and are purged to the sewer along with filtrate from this samefirst stage. Pulp is thoroughly washed as it leaves the first acidicstage of bleaching to prevent any entrained liquor containingsolubilized metals from being carried into later stages of bleaching. Ifnot adequately removed in the first acidic stage of bleaching, manganeseand iron can affect bleaching in the later stages by limiting brightnessdevelopment and increasing chemical consumption.

In U.S. Pat. No. 4,039,372, Reeve et al. included a fresh water wash onthe first acidic bleaching stage washer which prevents possiblecarryover of metals to the later stages of bleaching. A second freshwater wash volume was used after the final stage of bleaching. In thismanner, two wash volumes of fresh water must be evaporated as comparedto evaporation of only one wash volume if bleach plant filtrates are notrecovered.

Counter-current pulp washing with bleach filtrates can result in theaccumulation of calcium and magnesium in the bleach plant/brown stockwashing systems due to adsorption of metals on pulp at high pH andre-dissolving at low pH. This accumulation of calcium and magnesium canresult in the deposition of inorganic and organic matter on pulp andequipment which can increase bleach chemical consumption and requiredown time for equipment cleaning. Reeve et al. described the problems ofscaling and lignin deposition if calcium is not removed when practicingthe art of recovering bleach filtrates. To avoid this problem Reeve etal. used a portion of the filtrate from the first acidic stage ofbleaching in the causticizing plant thereby purging from the bleachplant some of the dissolved metals. This method of purging metals islimited by the volume of filtrate that can be used in causticizing.According to Reeve et al., approximately 325 gallons of the 1288 gallonsof first acidic stage filtrate is purged to the causticizing operationor about 25 percent. The remaining 75 percent of the filtrate from thefirst acidic bleaching stage is used to wash pulp on the deckerpreceding the bleach plant allowing the possibility for metals toaccumulate. Following the experience at Thunder Bay which incorporatedthis method of purging metals, Reeve noted that additional developmentwould be needed to adequately purge metals for the closed mill conceptto be feasible.

When recovering bleach plant filtrates, it is not possible to remove alldissolved organic matter entrained in the pulp from counter-currentdisplacement washing with bleach filtrates, before pulp enters thebleach plant. This is particularly true if fresh water usage is to belimited to keep evaporation requirements to a minimum. Reeve publishedlaboratory results documenting the increased bleach chemical consumptionthat results as the quantity of dissolved organic matter is increased inthe first stage of bleaching of a D-CE sequence at 70% chlorine dioxidesubstitution. This study showed that bleach chemical consumptionincreased as dissolved organic matter, removed from pulp in the D-Cstage, was re-introduced into the D-C stage, simulating the recovery ofbleach plant filtrates. The same conclusions were reached when dissolvedorganic matter, removed from pulp during the extraction stage, was addedto the D-C stage. Bleach chemical consumption increased more forextraction stage organic matter compared to D-C stage organic matter.Competition exists for bleaching chemicals in the first acidic stage ofbleaching between dissolved organic matter and lignin within the pulpfibers. As the quantity of organic matter added increases, increasingamounts of bleach chemicals in the first stage are consumednon-productively by the dissolved organic matter. This results in lessdelignification of the pulp as measured by the pulp kappa number.Following the experience at Thunder Bay, Reeve noted the need fordeveloping a bleaching sequence that minimized bleach chemicalconsumption due to dissolved organic matter carried into the bleachplant as a result of counter-current displacement pulp washing.

Recently published investigations on recovering chlorine-based bleachplant effluent have concluded that recovery of these effluents alongwith the pulping liquors in the conventional recovery process is nottechnically feasible. Others have published investigations on separaterecovery operations for pulping liquors and bleach plant effluent.

No process has since been developed that comes close to a substantialrecovery of bleach plant filtrates. In fact, based on a recentpublication (Paper ja Puu-Paper and Timber; 5/89), several Pulp andPaper Research Institutes in Scandinavia concluded that closure of thebleach plant was not likely to be available technology for at leastanother decade and would be dependent upon significant developments inboth pulp bleaching and in chemical recovery.

It would therefore represent a notable advance in the state of the artif a new process for recovering chlorine-based bleach plant effluents ina conventional pulping liquor recovery operation could be developedwhich provides very low chloride concentrations in the recovery process;little or no significant impact on evaporation requirements; morecomplete non-process metal removal; and negligible impact on bleachchemical consumption due to recovery of bleach filtrate.

SUMMARY OF THE INVENTION

The method of the present invention integrates advances in bleachingtechnology as well as in washing and recovery into a process thatpermits the substantial closure of the bleach plant while avoiding theproblems previously encountered.

The process of the present invention provides for the bleaching of woodpulp and for the recycling and recovery of bleach filtrates in a mannerthat will allow for: 1) the production of pulp with acceptablebrightness and quality; 2) the reduction of dissolved solids normallydischarged with bleach effluents including chlorinated organic material;3) minimal increase in the amount of water required to be evaporated; 4)no increased build-up of chlorides in the pulping liquor regenerationcycle; and 5) removal of non-process metals to prevent scale formation.

The process of the present invention accomplishes the foregoingobjectives by the following combination of sequences:

A bleaching sequence which provides a minimal chloride content of therecovered filtrates is effected by minimizing first the requirements formolecular chlorine and secondly chlorine dioxide. This is accomplishedpreferably with the use of oxygen delignification of either softwood orhardwood pulps obtained from the Kraft pulping process. Aftersignificant lignin reduction is achieved with the oxygen delignificationsystem, the pulps are then treated successively with a chlorine dioxide(D) stage, a peroxide reinforced oxidative extraction (EOP) stage, andat least one final chlorine dioxide (D) stage. The first acidic bleachstage can be 100% chlorine dioxide, chlorine dioxide with 10% or lessmolecular chlorine added or ozone. The final treatment can be either onestage (preferably for the production of 80-88 brightness targets) or twostages (preferably for the production of 90+ brightness).

The first chlorine dioxide stage is preferably operated at mediumconsistency; i.e., within the range of 8-14% and at a reduced pH of2-2.5.

An acid treatment stage is preferably introduced after oxygendelignification. The acid treatment stage is preferably placed afteroxygen delignification and before the first chlorine dioxide stage. Thisstage is introduced for the purpose of removing non-process metals suchas potassium, magnesium, calcium, manganese, iron, aluminum, and thelike.

The pulp from the first chlorine dioxide stage is neutralized by mixingwith the extraction stage filtrate. This neutralization allows for thedegassing of the pulp which enhances the effectiveness of the deckerwhich follows it, thereby allowing for a more effective operation. Also,this neutralization effectively utilizes residual alkali in theextraction stage filtrate and combines the filtrates from the firstchlorine dioxide and extraction stages.

Recycling of the combined acid filtrate from the first chlorine dioxidestage and the caustic extraction stage filtrate is conducted in acountercurrent fashion back through post oxygen delignification andbrown stock washing. The organic solids from these filtrates areeventually processed in the mills' recovery boiler where they aredestroyed through combustion. This recycling is accomplished with onlyan 8 to 10% increase in evaporator loading.

Removal of sodium chloride from the recovery boiler is accomplishedpreferably through the collection of the catch from the electrostaticprecipitator followed by an aqueous leaching of this catch to allow forthe separation of salt cake and sodium chloride. The salt cake isrecycled back to the black liquor feed and the chloride-rich aqueousmaterial is sewered.

By combining these various steps, the present invention allows for asignificant reduction in color, AOX, BOD and solids discharged in theeffluent associated with bleaching of chemical pulp to a degree thatrepresents a significant improvement relative to current practice.Furthermore, the present invention accomplishes this in a manner thatrepresents a significant improvement over previously developedtechniques that attempted various approaches for bleach filtraterecovery.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of the overall pulp making andchemical recovery processes in accordance with the present invention;and

FIG. 2 is a schematic illustration of the bleach plant operationincluding the filtrate recycling process of the present invention.

FIGS. 3 and 4 depict, in graphic form, the percent removal of variousmetals from hardwood and softwood pulps as a function of the pH in theacid treatment stage.

DETAILED DESCRIPTION OF THE INVENTION

The process of the present invention overcomes the previouslyencountered problems of high chloride concentration in the recoveryprocess by maintaining chloride concentration at or near currentoperating conditions of typical "inland mills". The process of thepresent invention achieves this low chloride concentration in therecovery process by limiting chloride input to the recovery process withbleach plant filtrates and reducing the cyclic flow of chloridetypically contained in the boiler ash.

Chloride input to the recovery process is limited by reducing the amountof chlorine-based bleach chemicals used in the bleach plant. In oneinstance, use of chlorine-based chemicals is reduced in the firstchlorine dioxide stage by incorporating stages of oxygendelignification, 100% chlorine dioxide substitution and hot oxidativeextraction with peroxide into the process. Chloride input to therecovery process is also reduced by recovering only the filtrates fromthe first chlorine dioxide stage and extraction stage in the OD(EOP)Dbleaching sequence.

The present process recovers only the filtrates from the first chlorinedioxide stage and EOP stage. The final chlorine dioxide stage filtrateis not recovered as this would more than double the quantity of chloridesent to the recovery process for only a 10% to 15% reduction in theenvironmental impact of the bleach plant effluent.

The final chlorine dioxide stage filtrate instead can be recovered byincorporating new cooking techniques such as extended modifiedcontinuous cooking or rapid displacement heating methods for batchcooking and enzyme prebleaching. By incorporating these techniques thetotal chloride in all filtrates of the OxD(EOP)D bleaching sequence isreduced such that recovery of all filtrates can be achieved whilemaintaining chloride concentrations of current "inland" mills. Completerecovery of bleach plant filtrates can be accomplished by replacing thehot wash water used on the (EOP) stage washer with filtrate from thefinal chlorine dioxide stage washer.

Chlorides feeding the boiler and circulating in the liquor cycle aregreatly reduced by incorporating a system to remove chloride from theboiler ash. Sodium chloride has a significant vapor pressure at theoperating temperatures of the boiler and as such chloride feeding theboiler is preferentially distributed in the boiler ash. Ash, beingre-dissolved in black liquor and fed to the boiler, creates asignificant cyclic flow of chloride. The subject process avoids thiscyclic flow of chloride by removing chloride from the ash before it isre-introduced to the boiler. The process also provides significantbenefit in the removal of potassium from the liquor cycle. The removalof chloride and potassium provides significant benefit to the recoveryboiler operation.

By limiting the amount of chlorine dioxide used in the bleach plant,which limits the chloride introduced into the pulping liquor cycle, andavoiding the cyclic flow of chloride contained in the boiler ash, thechloride concentration in the pulping liquor cycle and feed to therecovery boiler is maintained at normal levels. Typical chlorideconcentrations in white liquor and feed to the recovery boiler arecontrasted in Table 1 for four mills. A typical "inland mill" is onethat does not transport their wood supply via sea water. The "coastalmill" is one that does use sea water for wood supply transportation,such as some mills on the west coast of Canada. Results from the ThunderBay mill are reported literature values when that mill operated with theclosed mill concept. The results for mills operating according to thepresent invention are calculated for an "inland mill" operating with thebleach filtrate recovery process shown in FIG. 1 and FIG. 2. As shown inTable 1, the process of the present invention reduces the chloride inputto the liquor recovery operation by about 90% over that described byReeve et al in U.S. Pat. No. 4,039,372.

The present invention also provides a method for removing metals. In oneembodiment, the present process uses an acid treatment step to removemetals as illustrated in FIG. 2. An alternate process for removingmetals (not illustrated) utilizes sodium carbonate and/or sodiumhydroxide and/or green liquor from the pulping liquor recovery processto cause metal carbonates and metal hydroxides to precipitate from aportion of the first acidic bleach stage filtrate.

According to FIG. 2, an acid treatment stage is located after postoxygen delignification washing. The entire pulp stream is firstacidified to about 2 pH and then washed before it enters the chlorinedioxide stage of bleaching. Wash water from the acid treatment washingalong with the solubilized metals are discharged to the sewer. FIGS. 3and 4 illustrate the percent removal of various metals from hardwood andsoftwood pulps at different pH values in the acid treatment stage.Nearly complete removal of troublesome metals such as calcium, magnesiumand manganese is effected in this manner. With the acid treatmentsystem, described above and shown in FIG. 2, metals are removed beforefiltrates are recycled thereby overcoming all of the problems associatedwith metals noted previously. In addition, by using the acid treatmentstage, the need for a fresh water wash on the first acidic bleach stagewasher to prevent metals from being carried into later bleaching stagesis eliminated. Eliminating the need for a fresh water wash on this firstacidic stage avoids additional evaporation requirements. Wash water usedto wash the acid treated pulp is discharged to the sewer rather thanbeing evaporated.

Location of the acid treatment stage after oxygen delignification andpost oxygen washing is critical in enhancing the recovery of spentchemicals and dissolved organic matter from the wood pulp. This improvedrecovery is illustrated in Table 2 which shows how sewer losses vary ifthe acid treatment process is located before oxygen delignificationversus after oxygen delignification. Percent metal removal is the sameregardless of location. As shown in Table 2, nearly 25 times as muchcolor and 40 times as much total organic carbon (TOC) is lost to thesewer if the acid treatment is placed before oxygen delignificationrather than after oxygen delignification. At high chlorine dioxidesubstitution the entire softwood bleach plant discharges about 50 to 60#/T color. Placement of acid treatment before oxygen delignificationwould nearly negate the environmental benefit of recovering bleachfiltrates.

The process of the present invention is described here and shown in FIG.2 for medium consistency operation in the first chlorine dioxide stageof the OD(EOP)D sequence. The present process is equally applicable forlow consistency operation in the first chlorine dioxide stage byremoving the neutralization step shown in FIG. 2 and recycling chlorinedioxide filtrate from the first stage to the discharge of the highdensity storage tower as dilution to low consistency. In this case someextraction stage filtrate is used as a displacement wash on the firstchlorine dioxide stage washer with the remaining extraction stagefiltrate being used as displacement wash on the last post oxygen stagewasher.

Metals can also be removed by an alternate process which precipitatesmetals as carbonates and hydroxides. Metals, which enter the bleachplant absorbed to pulp at high pH, are dissolved in the low pH aqueoussolution of the first acidic bleaching stage. Any fraction of theaqueous filtrate from the first acidic stage of bleaching can be treatedin the precipitation process; however, 25% is adequate to removesufficient quantity of metals to prevent their detrimental effects onbleaching and scale deposition.

In this metal precipitation embodiment a fraction of the first acidicfiltrate is treated with sodium hydroxide and/or sodium carbonate, orgreen liquor from the pulping process, sufficient to raise the pHbetween 9 and 11 and provide an amount of carbonate ion such thatinsoluble metal carbonates and hydroxides will be formed. The aqueoussolution is maintained for 10 minutes at a temperature of from about130° F. to about 160° F. Under these conditions, with adequate carbonateions present, insoluble metal carbonates and hydroxides of calcium,magnesium, manganese and iron precipitate from the aqueous solution.

A suitable separation device, preferably a precoat filter or aclarifier, is used to separate the aqueous phase from the solidprecipitate. The solid precipitate can then be disposed of by landfillor introduced into the pulping liquor cycle either with heavy blackliquor before combustion in the recovery boiler or with green liquor. Ifthe precipitate is introduced into the pulping cycle, the non-processmetals will be removed from the mill along with other nonprocess metalsin the current practice of grits and dregs removal.

The aqueous phase from the separation device is then preferably reusedin the bleaching operation. This aqueous phase is relatively free ofmetals and can be used in the first acidic bleach stage washer todisplace entrained liquor containing metals. This method of washing pulpwith metal free filtrate reduces the quantity of metals carried into theextraction stage without the use of fresh water. Use of filtrate fromthe metal removal system is not limited to washing after the firstacidic bleach stage. It can also be used for pulp dilution prior to thehigh density storage or for washing pulp prior to bleaching.

Table 3 illustrates the results of a water balance around the bleachplant for a 500 T/D pulp mill incorporating the process illustrated inFIG. 1. The recovered filtrate volume from the bleach plant is 515gallons per minute (stream 40 in FIG. 1). This represents approximatelyan eight to fourteen percent increase in evaporation load as compared toa 500 T/D pulp mill that does not recover bleach filtrates. The reducedevaporation load of the present process compared to the processes of theprior art is the result of less water usage in the bleach plant. Thereduced water usage in the present process results from the use of twoextraction stage washers and avoiding the need for fresh water on thechlorination stage washer to wash the pulp free of entrained metals. Useof two extraction stage washers allows a reduced shower flow to achievethe same degree of washing.

In the present process, combined filtrates from the first chlorinedioxide stage and extraction stage are recycled counter-currently topulp flow for the purpose of reducing the entrained black liquor frombeing carried into the first chlorine dioxide stage (see FIG. 2). Whilethis displacement washing process prevents black liquor from beingcarried into the first chlorine dioxide stage, organic matter from thecombined filtrates, used to displace black liquor, are carried into thefirst chlorine dioxide stage. Carryover of the combined bleach filtratescan be reduced by squeezing the pulp to high consistency and/or carefuluse of fresh water for pulp washing. Limiting the amount of organicmatter carried into the first stage of bleaching will reduce the bleachchemical consumption by organic matter.

When organic matter from the combined filtrate (D1OO+EO) of the presentprocess is added to the first chlorine dioxide stage a small amount ofchlorine dioxide is consumed by the dissolved organic matter. Thisresults in reduced delignification in the first chlorine dioxide stageas shown in Table 4 by the increased kappa number as the amount of addedorganic matter increases. However this loss of delignification in thefirst chlorine dioxide stage may be corrected by oxygen in the oxidativeextraction stage as evidenced by the constant extracted kappa numbersshown in Table 4. Bleach chemical consumption by carryover of dissolvedorganic matter in the first acidic bleach stage is further reduced bycomplete substitution of chlorine dioxide for chlorine. Alsocontributing to the low chemical consumption in the first acidic stageof bleaching, by dissolved organic matter, is the highly oxidized natureof the organic matter having been exposed to oxygen and peroxide in theextraction stage. This means that for a given extracted kappa number,carryover of organic matter from the combined filtrate (D+EOP) of thepresent process into the first chlorine dioxide stage will not increasebleach chemical consumption.

The present process thereby avoids any increase in bleach chemicalconsumption due to the presence of dissolved organics by incorporatingoxygen and/or peroxide in the extraction stage of the bleach plant. Inthis manner one of the difficulties encountered while practicing the artof recovering bleach plant filtrates, as described in U.S. Pat. No.4,039,372, is unexpectedly avoided.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring to FIG. 1, Southern Pine Softwood (hardwood) Chips 10 arescreened (not shown) to remove oversized and undersized chips, thencooked in a digester 12 using the Kraft pulping process with a whiteliquor 14 charge of from about 15 to 22%, and preferably 18%, activealkali and about 20 to 40%, preferably about 30%, sulfidity undercooking conditions of about 310° to about 350° F., and preferably about344° F., and from about 80 psi to about 140 psi, and preferably about110 psi.

The resulting pulp having a Kappa number ranging from about 25 to about35, and preferably about 30, is discharged under pressure into a blowtank (not shown), then screened to remove uncooked knots (not shown).After removal of knots, the brown stock 16 is washed successively withfrom two to four stages, and preferably three stages of washing. Afterwashing, pulp is screened 20 to remove rejects and the resulting pulp 22is then charged to the oxygen delignification stage 32.

As best shown in FIG. 2, the pulp, after brown stock washing andscreening, is shown entering the last wash stage 26 prior to enteringthe oxygen delignification stage 32, wherein it is admixed with oxygen28 and oxidized white liquor 30 and then further delignified in anoxygen delignification stage 32 to a Kappa number ranging from about 14to about 20, and preferably about 16, corresponding to about 30 to about55%, and preferably about 45%, delignification. The oxygendelignification stage 32 is run under conditions of temperature(180°-210° F.) and pressure (90-100 psi) with alkali supplied in theform of the oxidized white liquor 30.

Following oxygen delignification, the pulp is again washed successivelywith from 2 to 4 stages of washing (shown as 34 and 38) to remove thelignin and inorganic materials. The wash water 35 is derived from thewashings from the next subsequent wash stage 38. The final wash isderived from filtrate 40 obtained from the decker 42 after the firstbleach stage as described hereinbelow. The resulting washed pulp is thenstored in a high density (10-12%) storage vessel 44.

The filtrates from the post oxygen delignification washers, 34 and 38,are recycled back countercurrently as wash water through the pre-oxygendelignification washer 26 as best seen in FIG. 2. All of the organic andinorganic materials are eventually concentrated through a train of blackliquor evaporators 46 and sent to the recovery boiler 48 for combustion,as shown in FIG. 1.

As best seen in FIG. 1, the inorganic salts, recovered as smelt 50, aredissolved in water to form green liquor in liquid preparation 52, whichin turn is treated with calcium oxide to regenerate the white liquor 14fed to the digester 12. The calcium carbonate byproduct is burned in akiln (not shown) expelling carbon dioxide and regenerating calcium oxidewhich is used to regenerate the white liquor.

Throughout the pulping (including oxygen delignification), washing andrecovery processes, no organic or inorganic materials are intentionallydischarged and/or disposed of, with the exception of the small amount ofdregs that settle out in the green liquor clarifier and grits from thegreen liquor shaker (not shown).

Returning now to FIG. 2, the pulp from high density storage 44 is thensubjected to an acidification treatment in tank 54 equipped with mixer57. The pulp can be treated with sulfuric acid, hydrochloric acid,nitric acid or the like to a pH within the range of from about 2 toabout 3 entering tank 54 through a line 59. The primary function of theacidification treatment is to solubilize the non process metals thatcome in with the wood supply and which must be purged from the process.In the past, this typically was done in the first acidic bleaching stagewhere the filtrate was discharged to the sewer. By adding an acidicstage with no ability to delignify, the metals can be removed andthereby allow the first acidic bleaching stage with its content ofsolids (color, BOD, etc.,) to be recovered. By acid treating the pulpfrom the high density storage not only are the metals removed but mostof the dissolved organics associated with the pulp slurry will beprecipitated onto the fibers and will be carried into the firstbleaching stage rather than discharged with the metals to the sewer.This is preferred to significantly reduce the discharge of dissolvedorganics. Accordingly, it can be seen that the acidification treatmentstep prevents the build-up of metals within the brownstockwashing/bleach plant cycle which would otherwise limit the viability ofthe process.

After acidification, the pulp is washed in washer 58 with fresh water toremove the acidic wash and the non-process metals. This wash, which islow in environmental impact since no bleaching or delignification iseffected, is discharged to the sewer at 60.

After the acid treatment and wash, chlorine dioxide or a mixture ofchlorine dioxide and chlorine is added to the pulp at an applicationrate of about 2.0 to 3.4%, preferably about 2.6%, calculated as activechlorine. The pulp is treated with the chlorine dioxide or a mixture ofchlorine dioxide and chlorine solution in the first bleaching stage 62under conditions of 10-12% consistency, a reaction time ranging fromabout 30 to about 90 minutes, preferably about 60 minutes, and atemperature ranging from about 100 to about 160° F., preferably about140° F. Although chlorine can be added along with the chlorine dioxidein the first bleaching stage, it is considered important in achieving ableaching stage with minimal chloride residuals to limit the use ofchlorine to less than about 10%, or completely eliminate the use ofmolecular chlorine.

After the first bleaching stage, the pulp is then discharged into amixing tank 64 for partial neutralization to a pH ranging from about 5to about 7, and preferably to about 7, using the alkaline filtrate 66from the first oxidative extraction stage 68 with some caustic make-upin the form of oxidized white liquor 65, generally less than 1% on pulp.The pulp is then thickened by passage over decker 42 and oxidized whiteliquor is added at an application rate of about 1 to about 2%. Hydrogenperoxide is then introduced to the stream from the decker and oxygen isadded to the pulp through high intensity mixer 70. Additionaldelignification is thus accomplished in oxidative extraction stage 68thereby producing a pulp with a Kappa number ranging from about 2 toabout 6, and preferably about 4. The pulp is then diluted at theoxidative extraction tower discharge using a portion of the filtrate 66from the first post extraction stage washer 72. Following the oxidativeextraction stage 68, the pulp is washed successively on two conventionalrotary drum washers 72 and 73. The pulp is then heated by steam in asteam mixer 74 and chlorine dioxide is added in a high intensity mixer76 and allowed to react in the chlorine dioxide bleaching tower 78 at atemperature ranging from about 150° to about 180° F., and preferablyabout 160° F., for from about two to about four hours, and preferablyfor about three hours.

The bleached pulp is then washed using paper machine white water with aportion of the filtrate being sewered at 80 and not recovered within theprocess. The remaining portion of the filtrate can be recycled to thechlorine dioxide bleaching tower 78 for pulp dilution. Thus, from thebleach plant 24, the only intentional discharges are flows from the acidpretreatment stage at 60 and from the final wash applied to the fullybleached pulp at 80.

Filtrate, from washing pulp exiting the oxidative extraction stage 68,is used, in part, for discharge dilution of the pulp from the oxidativeextraction tower 68 by way of line 66, and in part, is used forneutralization of the pulp exiting the first bleaching stage 62 inneutralization stage 64. Addition of fresh water to wash the pulp afterthe extraction stage is reduced by using two stages of washing and assuch is preferred to reduce, if not eliminate, additional evaporatorrequirements. Thus two stages of washing after the oxidative extractionstage is an important element to the viability of this process.

As shown in FIG. 2, filtrate 40 is produced when decker 42 thickens thepulp received from the neutralization stage 64. Filtrate 40, which is acombination of filtrate from the first chlorine dioxide stage andextraction stage, is used as wash water in the last post-oxygendelignification washer 38. The filtrate 35 from the last post oxygendelignification washer 38 is, as discussed, hereinabove, recycledcountercurrent to pulp through washers 34 and 26 via lines 35 and 33. Asshown in FIG. 1, filtrate 31 from washer 26 flows countercurrent to pulpthrough screening 20 and brown stock washing 18. In this way, chlorides,spent bleaching chemicals and organic matter removed during bleachingare combined with spent pulping liquor and evaporated producing strongblack liquor 84.

Chloride from the bleach plant, contained in black liquor 84 feeding therecovery boiler 48, is partially volatilized in the recovery boiler andcarried to the electrostatic precipitator 86 where it is collected andremoved with salt cake in the precipitator ash. This ash is dissolvedwith water in the salt leaching process at a temperature ranging fromabout 80° to about 120° F., and preferably about 100° F., to separateout sodium sulfate from sodium chloride. The aqueous sodium chloridesolution is sewered at 90 and the solid sodium sulfate 88, with someresidual chloride is recycled back to the mix tank 89. The leachingprocess prevents the build up of chloride concentration in the liquorcycle and maintains the concentration of sodium chloride in the whiteliquor at less than 5 grams per liter.

The leaching process as described herein operates at greater than 95%efficiency in terms of salt cake recovery.

Moreover, and most importantly, the improved process of the presentinvention wherein the filtrate from the peroxide reinforced oxidativeextraction (EOP) stage is recycled countercurrently through the bleachplant and brown stock washing and most preferably, wherein additionally,the filtrate from the first chlorine dioxide bleaching stage (D) is alsorecycled countercurrently through the brown stock washing, significantlyreduces the color, AOX and BOD in the bleach plant effluent as shown inTable 5 wherein the effects of chlorine dioxide substitution formolecular chlorine and the effect of the filtrate recycle in accordancewith the present invention are shown.

                  TABLE 1                                                         ______________________________________                                        COMPARISON OF TYPICAL CHLORIDE                                                CONCENTRATIONS FOR VARIOUS MILLS                                                        IN-             THUNDER    PRES-                                              LAND  COASTAL   BAY        ENT                                                MILL  MILL      MILL       MILL                                     ______________________________________                                        NaCl in White                                                                             3-6     25-50     50       4.5                                    liquor, grams                                                                 NaCl/liter                                                                    NaCl to Recovery                                                                          0.2-0.5 6.1       6.0      0.45                                   Boiler, % of                                                                  B.L. Solids                                                                   NaCl to recovery                                                                          1-3     11-36     115      10-12                                  process, pounds                                                               NaCl per ton pulp                                                             ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        COMPARISON OF SEWER DISCHARGE FROM ACID                                       TREATMENT OF SOFTWOOD PULP BEFORE AND                                         AFTER OXYGEN DELIGNIFICATION                                                  BEFORE OXYGEN    AFTER OXYGEN                                                 DELIGNIFICATION  DELIGNIFICATION                                              TO SEWER                    TO SEWER                                          H.sub.2 SO.sub.4                                                                          TOC     Color  H.sub.2 SO.sub.4                                                                         TOC   Color                             %     pH    #/T     #/T    %     pH   #/T   #/T                               ______________________________________                                        9.1   2.1   41.2    48.8   2.0   2.3  0.9   2.0                               ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        WATER BALANCE 500 T/D BLEACH PLANT WITH                                       BLEACH FILTRATE RECOVERY (FIG. 1)                                             Stream No.    Flow (gpm)                                                      ______________________________________                                        40            515                                                             41            148                                                             60            826                                                             63            1561                                                            67            735                                                             69             41                                                             71            104                                                             80            804                                                             82            557                                                             ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        EFFECT ON CHLORINATION AND EXTRACTED                                          KAPPA NUMBERS WHEN ORGANIC MATTER IS                                          ADDED TO THE CHLORINATION STAGE                                               (Combined Filtrate (D100 + EO) From Bleach Filtrate                           Recovery Added to First D Stage of OD(EO)D Sequence)                          Added Organic                                                                 Matter                                                                        % TOC on Pulp D100 Kappa Extracted Kappa                                      ______________________________________                                        0             6.3        4.1                                                   0.145        6.6        4.0                                                  0.29          7.0        4.3                                                  0.44          7.1        4.2                                                  ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        BLEACH PLANT EFFLUENT CHARACTERISTICS                                         BLEACH SEQUENCE COLOR      AOX     BOD.sub.5                                  ______________________________________                                        O(C + D.sub.10) (EO)D                                                                         120        8       30                                         O(D.sub.50 /C) (EO)D                                                                          90         4       25                                         OD(EO)D         50         2       20                                         OD(EO)D         10         1       10                                         OD(EO)D          1           0.1    2                                         ______________________________________                                         All values in lbs/ton                                                    

                                      TABLE 6                                     __________________________________________________________________________    ACID LEACHING OF OXYGEN DELIGNIFIED PULPS                                              Metals in Softwood Pulp, ppm                                                                             Metals in Hardwood Pulp, ppm                       Na  K   Mg  Ca  Mn  Fe Al  Na  K   Mg  Ca  Mn  Fe Al                 __________________________________________________________________________    As is    2765                                                                              273 572 1358                                                                              66  11 26  6498                                                                              667 382 2529                                                                              88  16 22                 After leaching                                                                          124                                                                               32  29  66  4   6  9   180                                                                               30  15  97  4   7  5                 % Removed                                                                               95  88  94  95 93  54 65   97  96  96  96 95  56 77                 __________________________________________________________________________

                  TABLE 7                                                         ______________________________________                                        Laboratory Bleaching of Oxygen Delignified Softwood Pulp                      With and Without Bleach Plant Filtrate Recycle                                Kappa number after oxygen                                                     delignification 14.2; Viscosity 15.1 cp.                                                     Without Recycle                                                                          With Recycle                                        ______________________________________                                        First Chlorine Dioxide State                                                  Chlorine dioxide,                                                                              3.13         3.13                                            % as active chlorine                                                          Chlorine dioxide,                                                                              1.19         1.19                                            % as chlorine dioxide                                                         Final pH         1.9          1.8                                             Oxidative Extraction State                                                    Sodium hydroxide 1.3          1.8                                             applied, %                                                                    Final pH         11.2         11.3                                            CEK No.          2.1          2.1                                             Brightness       52.4         51.1                                            Viscosity, cp    14.4         14.0                                            Second Chlorine Dioxide Stage                                                 Chlorine dioxide,                                                                              1.0          1.25                                            % as chlorine dioxide                                                         Final pH         3.2          3.1                                             Brightness.sup.1 86           86                                              Viscosity, cp    12.7         13.1                                            ______________________________________                                         .sup.1 Chlorine dioxide requirement to achieve 86 brightness interpolated     from several bleaching experiments.                                      

A laboratory simulation of the bleaching sequence with filtrate recycleas depicted in FIG. 2 was conducted. A mill softwood pulp (Kappa 14.2)taken from the second stage of post oxygen washing, similar to washer 38in FIG. 2, was bleached using the scheme in FIG. 2. In these runs sodiumhydroxide was substituted for oxidized white liquor. Fresh mill pulpfrom the second post oxygen washer was bleached in repeated runs.Filtrates from each run were saved and applied in the manner shown inFIG. 2 during the succeeding run. This was continued until equilibriumdissolved solids were established in the recycling filtrates. Chlorinedioxide was completely substituted for molecular chlorine in these runs.

Results of metal removal in the acid treatment stage are shown in Table6. The acid treatment stage was conducted at pH 2. More than 90% of thesodium, magnesium, calcium, and manganese present in the oxygendelignified and washed pulp was removed during acid treatment. Removalof potassium, iron and aluminum was lower, about 88% for potassium, 54%for iron and 65% for aluminum.

Bleach chemicals demand and final brightness achieved during theserecycle procedures are shown in Table 7 and are compared to labbleaching of the same softwood pulp without filtrate recycle. A modestincrease in both sodium hydroxide, 0.5%, and chlorine dioxide, 0.25%,was observed for the case of filtrate recycle compared to no filtraterecycle. Targeted brightness of 86 was achieved in both cases and pulpviscosity was similar.

The above-mentioned patents are hereby incorporated by reference.

Many variations of the present invention will suggest themselves tothose of ordinary skill in the art in light of the above-detaileddescription. All such obvious modifications are within the full intendedscope of the appended claims.

We claim:
 1. A process for bleaching Kraft wood pulp comprisingsubjecting the wood pulp after brown stock washing to the followingsteps conducted in sequence:oxygen delignification in the presence ofoxygen and oxidized white liquor followed by one to two stages of postoxygen washing; subjecting the oxygen delignified pulp to an acidtreatment at a pH of about 2 to 4 to substantially remove non-processmetals and washing the treated pulp with fresh water and discharging atleast a portion of the filtrate from said washing to the sewer;bleaching in a first chlorine dioxide stage where consistency ismaintained from about 9% to 14% and pH is about 2 to 4; partiallyneutralizing pulp, from said first chlorine dioxide bleaching stage, toa pH of 5 to 7 in a neutralization tank with filtrate from a subsequentoxidative extraction stage and with oxidized white liquor; thickeningpulp on a decker after which oxidized white liquor is added to raise thepH to about 10 to 13 and oxygen and hydrogen peroxide bleachingchemicals are added; subjecting the thickened pulp and bleachingchemicals to a hot extraction stage; thoroughly washing pulp from saidextraction stage with fresh water on two sequential washing stages tominimize the wash volume; subjecting said washed pulp to one or twofinal chlorine dioxide bleaching stages and thoroughly washing pulpafter each stage with either fresh water or paper machine white water ora combination of both; discharging to sewer the filtrate from saidwashing, after each said final chlorine dioxide stage; using filtratefrom said two stage sequential washing stages, after said extractionstage, to dilute and neutralize pulp from said first chlorine dioxidestage of bleaching in said neutralization tank such that filtrate fromthe extraction stage and the first chlorine dioxide stage are combinedwith pulp; separating the combined filtrates from the pulp on saiddecker and at least a portion of the filtrate is recycled to the lastwasher of the post oxygen washing stage as wash water; recoveringfiltrate from said last washer of the post oxygen washing stage in thecooking liquor recovery process by recycling countercurrently throughbrownstock washing constituting a weak black liquor which is evaporatedto produce a strong black liquor; combusting said strong black liquor ina recovery boiler to produce a smelt and a flue gas such that chloridefrom the recovered bleach plant filtrate is preferentially enriched inthe flue gas from combustion; collecting particles containing chlorideand sulfate in said flue gas as ash in an electrostatic precipitator;removing chloride and potassium from said ash by either leaching withwater or by evaporation crystallization from a water solution to producea solid stream of sodium sulfate and a salt solution rich in chlorideand potassium; discharging the salt solution to the sewer or recoveringit for its chlorine value; mixing said solid sodium sulfate with saidstrong black liquor prior to combustion in said recovery boiler; anddissolving said recovery boiler smelt in water to form green liquor andconverting it to pulping liquor in the causticizing process.
 2. Aprocess as defined in claim 1 wherein said first chlorine dioxide stageis operated at 2% to 5% consistency after which the pulp is thickened onsaid decker without washing before entering the oxidative extractionstage and using filtrate from said thickening process to dilute pulpbefore it enters said first chlorine dioxide bleaching stage whereby alldissolved solids and water entering or generated in the first chlorinedioxide stage passes into the oxidative extraction stage with the pulpfrom said decker; and wherein all filtrate from said first chlorinedioxide stage and said oxidative extraction stage are recovered byrecycling all filtrate from the oxidative extraction stage as wash waterto countercurrently wash pulp first on the post oxygen stage washers andthen the brownstock washers.
 3. A process as defined in claim 2 whereinall filtrates from the bleach plant are recovered by introducing freshwater only on the final chlorine dioxide bleaching stage washer andcountercurrently washing pulp from each preceding bleach stage withfiltrate from each succeeding bleach stage and continuing thiscountercurrent pulp washing for post oxygen washing and brownstockwashing.
 4. A process as defined in claim 1 wherein all filtrates fromthe bleach plant are recovered by introducing fresh water only on thefinal chlorine dioxide bleaching stage washer and countercurrentlywashing pulp from each preceding bleach stage with filtrate from eachsucceeding bleach stage and continuing this countercurrent pulp washingfor post oxygen washing and brownstock washing.
 5. A process forbleaching Kraft wood pulp comprising subjecting the wood pulp afterbrown stock washing to the following steps conducted in sequence:oxygendelignification in the presence of oxygen and oxidized white liquorfollowed by one to two stages of post oxygen washing; subjecting theoxygen delignified pulp to a first chlorine dioxide bleaching stagewhere consistency is maintained at 2% to 5% and pH is about 2 to 4;thickening pulp from said first chlorine dioxide tower on a decker,without washing with fresh water, after which oxidized white liquor isadded to raise the pH to about 10 to 13 and adding oxygen and hydrogenperoxide bleaching chemicals; subjecting the thickened pulp andbleaching chemicals to a hot extraction stage; thoroughly washing pulpfrom said extraction stage with fresh water on two sequential washingstages to minimize the wash water volume; subjecting said washed pulp toone or two final chlorine dioxide bleaching stages and thoroughlywashing pulp after each stage with either fresh water or paper machinewhite water or a combination of both; discharging to the sewer thefiltrate from said washing, after each said final chlorine dioxidestage; using a portion of filtrate from said thickening processfollowing said first chlorine dioxide bleaching stage to dilute pulpfrom said last washer of the post oxygen stage; treating a portion ofsaid filtrate from said first chlorine dioxide stage washer with sodiumhydroxide and sodium carbonate to effect precipitation of metals thatenter the bleach plant with the wood fiber; separating the precipitatedmaterial from the aqueous phase by gravity settling or filtration;disposing the precipitated sludge and using the metal free clarifiedfiltrate to wash pulp on the first chlorine dioxide stage washer toprevent the carryover of metals to the extraction stage whereby alldissolved solids entering or generated in the first chlorine dioxidebleach stage must either pass to the oxidative extraction stage with thepulp or be disposed of with the precipitated metal sludge; usingfiltrate from said at least two stage sequential washing stages as washwater to countercurrently wash pulp beginning with the last washer ofthe post oxygen stage and continuing through brownstock washing whichconstitutes a weak black liquor; evaporating said weak black liquor toproduce a strong black liquor; combusting said strong black liquor in arecovery boiler to produce a smelt and a flue gas whereby chloride fromthe recovered bleach plant filtrate is preferentially enriched in theflue gas from combustion; collecting particles containing chloride andsulfate in a said flue gas as ash in an electrostatic precipitator;removing chloride and potassium from said ash by either leaching withwater or by evaporation crystallization from a water solution to producea solid stream of sodium sulfate and a salt solution rich in chlorideand potassium; discharging the salt solution to the sewer or recoveredfor its chlorine value; mixing said solid sodium sulfate with saidstrong black liquor prior to combustion in said recovery boiler; anddissolving said recovery boiler smelt in water to form green liquor andconverting it to pulping liquor in the causticizing process.
 6. Aprocess as defined in claim 5 wherein said first chlorine dioxidebleaching stage is operated at 9% to 14% consistency after which thepulp slurry is diluted with filtrate from thickening on the succeedingsaid decker, without washing with fresh water, before entering theoxidative extraction stage; and wherein a portion of said filtrate fromsaid first chlorine dioxide stage thickening process is treated withsodium hydroxide and sodium carbonate to effect precipitation of metalsthat enter the bleach plant with the wood fiber; and wherein theprecipitated material from the aqueous phase is separated by gravitysettling or filtration; and wherein the precipitated sludge is disposedof and the metal free clarified filtrate is used to wash pulp on thefirst chlorine dioxide stage washer to prevent the carryover of metalsto the extraction stage whereby all dissolved solids entering orgenerated in said first chlorine dioxide bleach stage must either passto the oxidative extraction stage with the pulp or be disposed of withthe precipitated metal sludge; and further wherein all filtrates fromsaid first chlorine dioxide stage and said oxidative extraction stageare recovered by recycling all filtrate from the oxidative extractionstage as wash water to countercurrently wash pulp first on the postoxygen stage washers and then the brownstock washers.
 7. A process asdefined in claim 6 wherein all filtrates from the bleach plant arerecovered by introducing fresh water only on the final chlorine dioxidebleaching stage washer and countercurrently washing pulp from eachpreceding stage with filtrate from each succeeding bleach stage andcontinuing this counter current pulp washing for post oxygen washing andbrownstock washing.
 8. A process as defined in claim 6 wherein greenliquor is used to effect the metal precipitation from the first chlorinedioxide bleaching stage.
 9. A process as defined in claim 6 wherein acombination of green liquor, sodium hydroxide and sodium carbonate isused to effect the metal precipitation.
 10. A process as defined inclaim 6 wherein the metal precipitate is mixed with said strong blackliquor before combustion or added to green liquor for removing metalswith grits and dregs.
 11. A process as defined in claim 5 wherein allfiltrates from the bleach plant are recovered by introducing fresh wateronly on the final chlorine dioxide bleaching stage washer andcountercurrently washing pulp from each preceding stage with filtratefrom each succeeding bleach stage and continuing this counter currentpulp washing for post oxygen washing and brownstock washing.
 12. Aprocess as defined in claim 11 wherein green liquor is used to effectthe metal precipitation from the first chlorine dioxide bleaching stage.13. A process as defined in claim 11 wherein a combination of greenliquor, sodium hydroxide and sodium carbonate is used to effect themetal precipitation.
 14. A process as defined in claim 11 wherein themetal precipitate is mixed with said strong black liquor beforecombustion or added to green liquor for removing metals with grits anddregs.
 15. A process as defined in claim 5 wherein green liquor is usedto effect the metal precipitation from the first chlorine dioxidebleaching stage.
 16. A process as defined in claim 15 wherein the metalprecipitate is mixed with said strong black liquor before combustion oradded to green liquor for removing metals with grits and dregs.
 17. Aprocess as defined in claim 5 wherein a combustion of green liquor,sodium hydroxide and sodium carbonate is used to effect the metalprecipitation.
 18. A process as defined in claim 17 wherein the metalprecipitate is mixed with said strong black liquor before combustion oradded to green liquor for removing metals with grits and dregs.
 19. Aprocess as defined in claim 5 wherein the metal precipitate is mixedwith said strong black liquor before combustion or added to green liquorfor removing metals with grits and dregs.